Silica pigment and elastomer-silica pigment masterbatches and production processes relating thereto

ABSTRACT

As indicated at (A) through (D-6) of the drawings, the invention first produces an aqueously wet silica pigment composition (D-1) which in the embodiments is treated with oleophilic material (B) and/or reactant (C). The so treated compositions (D-1) are suitable for masterbatching with elastomer in solvent dispersion (E)-(FIG. 1) or aqueous dispersion (E&#39;&#39;)-(FIG. 2) with or without prior reduction or removal of free water (D-2). The silica pigment composition (D-2) is blended (at D-3) with carbon black pigment and/or processing oil (M) and, with adjusted water content, these combinations are formable into pigment beads (via D-4, D-5, D-6). The overall process curbs the losses of pigments in the masterbatching and promotes uniformity of product, The silica pigment compositions (D-1), and especially (D-3) when beaded, constitute pigment materials useful for the compounding of rubber.

United States Patent [191 Burke SILICA PIGMENT AND ELASTOMER-SILICA PIGMENT MASTERBATCHES AND PRODUCTION PROCESSES RELATING THERETO 21 App]. No.: 269,784

Related U.S. Application Data [60] Continuation-in-part of Ser. Nos. 216,948, Jan. 11, 1972, Pat. No. 3,700,690, and Ser. No. 55,458, July 16, 1970, Pat. No. 3,686,113, and Ser. No. 55,459, July 16, 1970, Pat. No. 3,686,219, and Ser. No. 55,479, July 16, 1970, Pat. No. 3,694,398, said Ser. No. 216,948, is a continuation-in-part of Ser. No. 55,384, July 16, 1970, abandoned, and Ser. No. 55,476, July 16, 1970, abandoned, said Ser. No. 55,458, and Ser. No. 55,459, and Ser. No. 55,479, and Ser. No. 55,384, and Ser. No. 55,476, each is a continuation-in-part of Ser. No. 798,215, Sept. 16, 1968, abandoned, which is a division of Ser. No. 611,250, Jan. 24, 1967, Pat. No. 3,523,096, which is a continuation-in-part of Ser. No. 458,420, May 24, 1965, abandoned, and Ser.. No. 458,379, May 24, 1965, abandoned, and Ser. No. 479,806, Aug. 16, 1965, Pat. No. 3,401,017.

[52] U.S. Cl 106/288 B, 106/308 N, 106/308 F, 106/308 Q, 106/307, 260/336 A0 [51] Int. Cl C08c 11/10, C08d 9/00 [58] Field of Search 106/288 Q, 288 B, 308 N, 106/308 F, 308 Q; 260/336 A0 Oct. 8, 1974 [56] References Cited UNITED STATES PATENTS 2,663,650 12/1953 Iler 106/308 Q 3,392,140 7/1968 Moahs et a1. 260/415 3,686,219 8/1972 Burke 106/308 N 3,686,220 8/1972 Burke 106/308 N Primary Examiner-Delbert E. Gantz Assistant ExaminerJ. V. Howard Attorney, Agent, or Firm-Hall & Houghton [57] ABSTRACT As indicated at (A) through (D-6) of the drawings, theinvention first produces an aqueously wet silica pigment composition (D-l) which in the embodiments is treated with oleophilic niaterial (B) and/or reactant (C). The so treated compositions (D-l) are suitable for masterbatching with elastomer in solvent dispersion (E)-(F1G. 1) or aqueous dispersion (E)-(F1G. 2) with or without prior reduction or removal of free water (D-2). The silica pigment composition (D-2) is blended (at D-3) with carbon black pigment and/or processing oil (M) and, with adjusted water content, these combinations are formable into pigment beads (via D-4, D-5, D-6). The overall process curbs the losses of pigments in the masterbatching and promotes uniformity of product, The silica pigment compositions (D-l and especially (D-3) when beaded, constitute pigment materials useful for the compounding of rubber.

11 Claims, 2 Drawing Figures PATENIED UN 8 I874 SHEEIHFZ Oleophilic material selected from:

(I) the oleophilic amines; (II) the oleophilic carboxylic acids; (III) the oleophilic carboxylic acid (A) salts of aluminum, zinc, the q wet never alkaline earth metals and dried sil Pigment ammonium hydroxide; p p having (IV) the oleophilic amine carboxylatcs; residual alkali content (V) the oleophilic quaternary ammonium compounds; (VI) the oleophilic hydroxy compounds; (VII) the combinations of 2 or more members of the foregoing groups.

Rcactant from members of (I) water soluble salts (13-1) -1 of aluminum or zinc, gwater soluble (II) water soluble salts and/or (B) polyol material of alkaline earth metals. and/0r (3-1) (III) water soluble acids (IV) combinations of 2 or I more such members I I 1 organic solvent Elastomer Red uction 3r immiscible with removal of water free water I l l r 1 (F) (M) Rlastomer (E' Comb ine (E) with 3 (l) cafrbon black dissolved in at least one from 4"." (D- I Plgment x solvent (3' g (13-6) Blend (2) Processing 01.1

A- (a) (w) Solvent removal water yielding coagulum I and aqueous serum (e.g. injecting (F) Heat I E 4) into hot water) orm Beads :Ieat

Mechanical separation of aqueous serum from con nl um 5) Drying of Beads Drying of Se: coagulum fre um essentially c pigment Fig. l

tsscrntially all employed the pigment PATENTELUET 81914 SHEEI 2 OF 2 Oleophilic material selected from:

(I) the oleophilic amines;

(II) the oleophilic carboxylic acids: (A) (III) the oleophilic carboxylic acid salts Aqueously wet never of aluminum, zinc, the alkaline dried silica pigment earth metals and ammonium hydroxide: precipitate having (IV) the oleophilic amine carboxylates; residual alkali content (V) h le phili q aternary ammonium compounds; (VI) the oleophilic hydroxy compounds; (VII) the combinations of 2 or more members of the foregoing groups.

I Reactant from members of I I (I) water soluble salts (D l) I of aluminum or zinc, I water soluble (A) w/wo (C) (II) water soluble salts and/or (B) P Y material of alkaline earth metals,

(III) water soluble acids (IV) combinations of 2 or more such members Combine (E' with at least one of (D-l) thru (D-6) Coagulum of elastomer and pigment prepared and/or (B-l) Reduction or removal of free water (1) Carbon black (D-3) pigment and/or Blend (2) Processing oil F'"""" x V water Form Beads 7 by comb ining (F and (C) I &

l I (D-S) 4 (I I Drying or Beads Heat Mechanical separation I of aqueous serum from coagulum (U-6) Beaded 2 Pigment WM Scrum essentially Drying of free coagulum f pigment mastcrbatc'h incorporating essentially all the pigment umnloved Dry elastomcr-silica pigment SILICA PIGMENT AND ELASTOMER-SILICA PIGMENT MASTERBATCHES AND PRODUCTION PROCESSES RELATING THERETO Serial No. Filed Case No. Patent No.

Zl6,948 .Ian. 11, 1972 48DM-2A CIP 3,700,690 55,458 July 16, 1970 48DM-2Q 3,686,113 55,459 July 16, 1970 48DM-3 3,686,219 55,479 July 16, I970 48DM-l2 3,694,398 55,384 July 16. 1970 48DM-l3 abandoned thesaid application Ser. No. 216,948 having been a continuation-in-part ol" the following two applications 48DM l3 now abandoned I 48DM-2A, now abandoned July 16, 1970 July 16, l970 and all'of said applications filed July 16. 1970 being continuations-in-part.of application 798,,215 Sept; 16, 1968 48DMDiv. 1 now abandoned itself a divisionsof application 611,250 Jan. 24, I967 48DM'now Patent which in turn was a continuation-in-part of earlier applications 458,420 -Ma.y 2.4, 1965 48D'now abandoned 458,379 May 24. 1965 48C now abandoned 479,806 Aug. I6, 1965 48E, now Patent the disclosures of all of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention The field to which this invention pertains is the preparation of unique silica pigment compositions which may be employed in the forming of masterbatches of such unique silica pigment compositions of elastomersand otherpolymeric materials.

2. Description of the Prior Art It is well known in the art that attempts to make mason the commercial market, nor have the unique silica pigment compositions and modes of preparing the same, provided by this invention, heretofore been: known.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 of the drawings are block-diagrams illustrative of the process aspects of the invention, with the overall process applied to the preparation of the pigment compositions and masterbatching thereof with elastomers in solvent and aqueous dispersions, respectively.

SUMMARY OF THE INVENTION It is known to those skilled in the art to prepare hydrated silica pigment for the reinforcement of rubber by precipitation from aqueous solutions of alkali metal silicates withthe aid of carbon dioxide, and to carry out such precipitation in manners to-avoid the formation of gelatinous masses-(i.e., the formation of silica gel)- and-to-promote the precipitation of a silica pigment in finely divided form (i;e., in particles in the reinforcing size range of about 0.015 to about 0.150 microns,

preferably 0.02 to 0.06 microns) and to recover the pigment from the resulting wet silica pigment by filtration, washing and drying.

The wet silica pigments formed by precipitation from alkali metalsilicate solutions with the aid of carbon dioxide have a boundalkali content in the range of about 0.1 to lO'percent by weight as Na O, and upon being dried in this state form aggregates, from the pigment particles of reinforcing size, which aggregates are of much greater than reinforcing size and will not adequately disperse (i.e., break down into particles of reinforcing size) when incorporated into rubber either by dry compounding orlatex'compounding.

When one treats such alkaline wet silica pigments with water soluble salts of alkaline earth, metals, e .g., calcium salts, to substantially replace the bound alkali metal of the silica, the resulting pigment, when dried, still evidences the formation of aggregates of greater than reinforcing size, which do not adequately disperse in the rubber. I

When one treats the alkaline wet silicapigments with the water soluble saltsof aluminum and/or zinc, to substantially replace the alkali metal content thereof, the resulting acidic. pigment, when dried, disperses to a greater extent in rubber, evidencingless aggregation than the neutral and alkaline products referred to above.

Finally, when one renders the wet silica pigment strongly acidic, by treatment with sulfuric acid and drying, the resulting strongly acidic product is more readily dispersible infrubber, and exhibits minimum aggregation; however, such highly acidic pigments are not practicable for use in the reinforcement of rubbers, since their acidity adversely effects vulcanization thereof. I

Thus the drying of the wet silica pigment in alkaline, neutral, and moderately acidic states, in each instance causes the formation of aggregates of pigment particles to a greater or lesser degree which aggregation prevents adequate dispersion of the dry pigment in the rubber; the formation of these-aggregates by the drying of the pigment is irreversible; and they remain mostly as aggregates that do not disperse in the rubber either by dry compounding or latex compounding.

This invention is based on the premise that uniformity of an elastomer-pigment masterbatch depends both on obtaining, incorporation of a measured quantity of pigment in the masterbatch (e.g., avoiding loss of pigment in the serum in wet masterbatching) and adequate dispersion of the pigment in the elastomer in particles of reinforcing size (e.g., minimizing the pigment aggregation problem); and the present inventionprovides a process" for accomplishing these ends by forming the masterbatch from aqueously wet hydrated silica pigment precipitates having a bound alkali content of 0.1 to 10 percent by weight as Na O; which has been prepared by precipitation from an aqueous solution of alkali metal silicate with the aid of carbon dioxide; and which has continuously been maintained in an aqueously wet state after its precipitation without having been dried therefrom; and which is combined with an elastomer dispersion in the still aqueously wet state, with special provisions for avoiding loss of pigment in the aqueous serum and promoting uniformity of product in the masterbatch.

Thus, the present invention, inter alia, provides a simple and efficient process for the curbing of silica pigment losses and the promotion of uniformity of product in the preparatfim of masterbatches of measured silica pigment content. As shown in the drawing, the first part of the process comprises the steps of:

A. providing to 75 parts by weight, dry basis, of aqueously wet hydrated silica pigment precipitate which has a bound alkali content in the range of 0.1 to

l0 percent by weight as Na O; which has been prepared by precipitation from an aqueous solution of alkali-metal silicate with the aid of carbon dioxide; and which has continuously been maintained in an aqueously wet state without having been dried therefrom after its precipitation;

B. providing a quantity of from 0.1 to 20 percent by weight, based on the silica pigment (A) dry basis, of oleophilic material selected from the members of Groups (l) through (VII) set forth at (B) in the drawing, and in more detail hereinafter;

C. providing reactant material selected from the class consisting of the members of Groups (I) through (IV) set forth in (C), and in more detail hereinafter;

D. combining the wet silica pigmentfrom (A)-with or without oleophilic materialfrom (B), and from 0 to at least a stoichiometric equivalent, based on the alkalinity of the silica pigment, dry basis, of reactant-from (C)--, thereby to form an aqueously wet silica pigment composition (D-l The silica pigment composition so provided, particularly when it contains the oleophilic material from (B), may be dried to yield useful dispersible dry silica pigment compositions as indicated at (D-2), or may be used without drying, eg in the second part of the masterbatching process, by process routes (E) to (L)-(FIG. l) or (E) to (L)-(FIG. 2), hereinafter described.

The silica pigment compositions (D-l) with or without (B) and/or (C), together with from 0 to percent based on the silica pigment, dry weight, of water soluble polyol material (B-l may have its content of water reduced as indicated at (D-2), e.g., by drying, pressing, centrifuging, or mixing with previously prepared dry silica pigment, and may be blended (at D-3) with at least 5 percent by weight, based on the pigment, of carbon black and/or processing oil eg in the ratio of about 5 to 75 parts silica pigment (D-2) dry basis, by weight to about 5 to 75 parts carbon black and/or about 5 to 45 percent by weight of processing oil (M), based on the combined weight of silica and carbon black, and the water having been adjusted, as aforesaid by addition of water (W), to approximately equal the weight of the non-aqueous part of the blend (D-3), i.e., in the range of about /z to 1% parts of aqueous phase per part of non-aqueous phase, so as to permit beading, the composition may be beaded in any suitable beading device, e.g., a laboratory beader, of the low shear cake mixer type, or in some instances, in a high shear Waring blender, or in others in such blender followed by the low shear beading, or in a commercial beading equipment, e.g. as described in Glaxner Reissue Patent No. 21,379 dated Mar. 5, 1940, and the resulting pigment beads (D-4) may be dried (D-S) to produce a beaded pigment (D-6) useful for the rubber trade.

In its presently most preferred embodiments the beading process comprises, in combination:

a. providing-at (A)-l0 weight parts, dry basis, of aqueously wet hydrated silica pigment precipitate which has a bound alkali content in the range of 0.1 to 10 percent by weight as Na O; which has been prepared by precipitation from an aqueous solution of alkali metal silicate with the aid of carbon dioxide; and which has continuously been maintained in an aqueously wet state without having been dried therefrom after its precipitation;

b. providingat (M)+from 0 to 150 weight parts, dry basis, of carbon black;

0. providing--at (M)from 0 to 45 percent based on the total of (a) and (b) dry basis, by weight of process ing oil;

d. replacing-at (D-1) from O to 100 percent of the alkalinity of the wet pigment provided in (a) by reaction with reactant selected from the class consisting of the members of the following groups: Group (I) the water soluble salts of aluminum or zinc; Group (II) the water soluble salts of alkaline earth metals; Group III) the water soluble acids; Group (IV) combinations of- 2 or more members selected from Groups (I), (II) or e. combining with said wet pigment (A) from 0 to 2 parts by weight of oleophilic material selected from the class consisting of the members of the following groups:

(I) the oleophilic amines; (II) the oleophilic carboxylic the oleophilic hydroxy compounds; (VII) the combinations of 2 or more members ofthe foregoing groups; and from O to 1 parts of polyol dry basis by weightfrom (B-l)-, to provide a silica pigment for use in steps (D2) to (D-6);

f. mixingat (D-3)the pigment provided by step (D-l) with at least /2 part of material selected from the group consisting of '(b), (c) and (e) in the presence of sufficient water to enable beading of the mixture (said quantity being adjusted as aforesaid), and

g. beading and drying the composition so formed-at (D-4) and (D5).

The wet silica pigment compositions (D-1) and (D-2) as above set forth, and (D-3), or (D-4), may be masterbatched in aqueously wet form with the elastomer in solvent-dispersion (E)-(FIG. l) or aqueous dispersion (E-l)-(FIG. 2).

In the case of the elastomer solution masterbatching (IEIG. l) the overall process comprises the further steps 0 E. providing an organic solvent dispersion of the elastomer containing l parts of the elastomer (E) by weight, and (2) the solvent (8) of which is essentially water immiscible, I

F. combining with the elastomer solution (E) the wet silica pigment composition (D-l), (D-2) and/or (D-3),

and (G) to (L) removing the solvent and aqueous phase and recovering the resulting combination as a masterbatch (L).

In FIG. 1', the elastomer (E') is dissolved in solvent (S')which may be recycled solventto form solution (E) and said solvent itself, or as an azeotrope with water, preferably has a boiling point lower than that of water at atmospheric pressure, and the viscosity of the elastomer-solvent dispersion (i.e., solution) (B) preferably should be selected in the range of 5,000 to 50,000 centipoises to facilitate the intimate blending as at (F), of the elastomer-solvent solution and the silica pigment composition (D-l (D-2) and/or (D3), which may be combined therewith in alkaline, essentially neutral, or acidic form as exemplified hereinafter.

The silica-elastomer masterbatch (L) is recovered in FIG. 1, by separating the volatiles from'the'coagulum, preferably in two steps (G) and (I), when the solvent or its aqueous azeotrope ca be volatilized in step (G) prior to separation of the solids from the remaining aqueous phase in step (I). The volatilizing of the solvent, step (G) to convert the mixture (F) to coagulum and aqueous serum may be effected by running the dispersion (F) into hot water. The greater part of the separation of the coagulum from the aqueous serum in step (I) is preferably effected by mechanical dewatering, e.g., filtration, decanting, centrifuging, etc., to reduce the heat requirement for final drying of the masterbatch. The serum removed by mechanical dewatering is found to be essentially free of silica pigment as indicated at (J) in the drawing and the dry elastomer-silica pigment masterbatch thus incorporates essentially all of the pigment employed. The process thus curbs silica losses and assures a uniform silica pigment content in the masterbatch.

In the case of the elastomer latex (i.e., aqueous dispersion) masterbatching (FIG. 2) the overall process comprises steps (E') through (L), there shown, namely:

E. providing an aqueous dispersion containing (1) 100 parts by weight of the elastomer and (2) from 0.5 to parts by weight of anionic dispersing agent;

F. forming a mixture of l) the aqueous elastomer dispersion-from (E), and'(2) the wet silica pigment composition (D-l (D-2) and/or (D-3), and (3) a sufficient quantity of the reactant material provided in step (c) to cause coagulation of the solids of the combination, whereby there is formed a coagulum of such solids rendering the. aqueous serum of the combination essentially free of silica pigment; and

G. to L. recovering the coagulum as a masterbatch.

As is shown in the drawings the recovery steps (I) through (L) in FIG. 2, corresponds to steps (I) through (L) of FIG. I, already described, and hence require no further description.

In certain preferred embodiments, (l) the solution masterbatch (FIG. 1) may be prepared from dry silica pigment compositions before or after beading (D-5) or (D-6), and (2) the latex masterbatches (FIG. 2) may also be prepared from silica pigment compositions before or after beading (D-S) or (D-6) by aqueously dispersing such dry pigment or dry pigment beads prior to masterbatching.

OLEOPHILIC MATERIALS The oleophilic materials employed in preferred em- GROUP (I) OLEOPI-IILIC AMINES The oleophilic amines are those meeting the following definition (A):

A. The oleophilic amines have from I to 10 primary and/or secondary and/or tertiary amine groups and not more than 36 carbon atoms per amine group and have at least one amine group attached to a chain of at least 8 carbon atoms and not more than 36 carbon atoms imparting oleophilic properties to the compound.

Oleophilic amines meeting this definition (A) are exemplified by the following categories:

A l. long-chain primary amines represented by the formula R-NH in which R contains from 8 to 36 carbon atoms and includes but is not limited to octyl amine, decyl amine, dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, palmitoleyl amine, oleyl amine, linoleyl amine, linolenyl amine, the mixed primary amines derived from fatty oils such as coco amine, soybean amine, tallow amine, rosin amine, and particularly or completely hydrogenated amines derived from the above unsaturated amines, and the like;

A 2. long-chain secondary amines having at least a single alkyl substituent containing from 8 to 36 carbon atoms, e.g., long-chain secondary amines represented by the formula in which R contains from 8 to 36 carbon atoms and R contains from I to 36 carbon atoms, and includes but is not limited to dioctyl amine, didecyl amine, didodecyl amine, ditetradecyl amine, dihexadecyl amine, dioctadecyl amine, dipalmitoleyl amine, dioleyl amine, dilinoleyl amine, dilinolenyl amine, the mixed secondary amines derived from fatty oils such as dicoco amine, disoybean amine, ditallow amine, hydrogenated ditallow amine, N-methyloctylamine, N- methyldodecylamine, N-methylhexadecylamane, N- ethyloctylamine, N-ethyloctadecylamine, N- propyldodecylamine, N-butyloctylamine, and the like.

A 3. long-chain tertiary amines having at least are alkyl or alkylene substituent containing from 8 to 36 carbon atoms, e.g., (a) long chain tertiary amines represented by the formula H V in which R contains 8 to 36 carbon atoms, R contains 1 to 36 carbon atoms and R contains 1 to 36 carbon atoms and includes but is not limited to trioctyl amine, tridodecyl amine, tristearyl amine, octydimethyl amine,

dioctyl methyl amine, dodecyl dimethyl amine, didodecyl methyl amine, octadecyl dimethyl amine, dioctadecyl methyl amine, the mixed tertiary amines derived from fatty oils, coco dimethyl amine, dicoco methyl amine, soybean dimethyl amine, disoybean methyl amine, tallow dimethyl amine, ditallow methyl amine, and the hydrogenated or partially hydrogenated products of unsaturated tertiary amines, and the like; and (b) long chain cyclic tertiary amines including but not limited to N-coco morpholine, N-soya morpholine, N- tallow morpholine and the like.

A 4. long-chain diamines and polyamines having at least one alkyl or alkylene substituent containing from 8 to 36 carbon atoms including, but not limited to, the diamines represented by the formula RNH(CH NH in which R contains 8 to 36 carbon atoms and x is an integer from 1 to 18, as for example N-cocotrimethylene diamine, N-soya trimethylene diamine, N-tallow trimethylene diamine, N-oleyl trimethylene diamine, N-octyl dimethylene diamine, N-octyl tetramethylene diamine, and the above diamines with one or more amine hydrogens replaced by a methyl, ethyl, propyl or butyl group, and the like.

A 5. long-chain polyethoxylated and polyproxylated secondary and tertiary amines containing at least one alkyl or alkylene substituent having from 8 to 36 carbon atoms e.g., the polyalkoxylated amines represented by the formulas N-(CHzCHzCHzO) 1 H in which R contains 8 to 36 carbon atoms and R contains l to 36 carbon atoms and x,, x x x y,, y, are each integers between 1 and 30, and include but are not limited to coco amine, soybean amine, tallow amine and stearyl amine each reacted with a plurality, eg 2, 5, l or 15, moles of ethylene oxide or propylene oxide per mole of amine; and the like;

A 6. long-chain polyethoxylated and polypropoxylated diamines having at least a single alkyl or alkylene substituent having from 8 to 36 carbon atoms e.g., the diamines represented by the formulas in which R contains 8 to 36 carbon atoms and x x y Y2 Z. and Z are each integers between 1 and 30, which include, but are not limited to, the reaction products of N-coco trimethylene diamine, N-soya trimethylene diamine and N-tallow trimethylene diamine each with a plurality, .e.g., 3, 10 or 20 moles of ethylene oxide or propylene oxide per mole of amine, and the like.

A 7. long-chain imidazolines and the like having at least a single substituent containing a chain of at least 8 carbon atoms, such for example those set forth in U.S. Pat. Nos. 1,999,989; 2,155,877; 2,155,878; 2,194,419; 2,267,965; 2,155,878; 2,355,837; 2,267,965; 2,708,666; 3,050,529; 3,408,361;

3,354,175; and 3,468,904, herein incorporated by reference.

Group (II) Oleophilic Carboxylic Acids and their alkali metal and ammonium water soluble salts.

The oleophilic carboxylic acids are those meeting the following definition (B):

B. The oleophilic carboxylic acids have from 1 to 10 carboxylic acid groups and have at least one carboxylic acid group attached to a chain of from 8 to 36 carbon atoms imparting oleophilic properties to the compound. Oleophilic carboxylic acids meeting this definition (B) are exemplified by the following category:

B l. the fatty acids and the rosin acids and derivatives thereof, which have from 1 to 10 carboxyl groups and a chain of from 8 to 36 carbon atoms attached to at least one carboxyl group thereof, and such long-chain carboxylic acids include the individual fatty acids such as caprylic, capric, lauric, myristic, palmetic, stearic, oleic, linoleic, linolenic, abietic, hydroabietic, dehydroabietic, ricinoleic, and the like; the naphthenic acids; the mixed fatty acids derived from vegetable oils such as coconut, palm, linseed, cottonseed, soya, tung, perilla, tall, corn, oiticica, and castor oils, and the like; the rosin and disproportionated rosin acids; the mixed fatty acids derived from animal fats such as tallow fatty acids; the mixed fatty acids derived from fish oils, such as herring, menhaden, salmon and sardine o i ls, and the like; the dimers, trimers, and tetramers of the foregoing unsaturated fatty acids such as the dimer acids from bodied soya bean oil, the trimer acids from bodied linseed oil, and the dimers, trimers and tetramers of fish oil fatty acids; and derivatives of the foregoing such as the partially and totally hydrogenated, hydroxylated, oxidized, epoxidized, halogenated, cyanoated, sulfurated, styrenated, and maleated (maleic anhydride) fatty acids, and the like. The saturated carboxylic acids are preferred.

Group (III) Oleophilic Carboxylic Acid Salts of Aluminum Zinc, the Alkaline Earth Metals and Ammonium Hydroxide.

The oleophilic carboxylic acid salts of this groups are those meeting the following definition (C):

C. the aluminum, zinc, alkaline earth metal, and ammonium saltsof oleophilic carboxylic acids which have from 1 to 10 carboxylic acid groups and have a chain of from 8 to 36 carbon atoms attached to at least one carboxyl group thereof imparting oleophilic properties to the compound. Oleophilic carboxylic acid salts meeting this definition (C) are exemplified by the following category:

C l. the aluminum, zinc, alkaline earth metal and ammonium salts of the oleophilic carboxylic acids set forth in category (B) (1) above.

19 Group (IV) Oleophilic A mine Carboxylates The oleophilic amine .carboxylates are those meeting the following definition (D):

D. The oleophilic amine carboxylates are the mem- .droxyl groups; morpholine and the substituted morpholines in which the substituents in the 4, 2, and 6 position of the morpholine maybe one or more methyl, ethyl, propyl and the like alkyl groups, hydroxy] groups or bers of the class consisting of (a) the neutrahbasic and amme l g other *l h'fwmg bolmllgpomts acidic carboxyliciacid salts of amines, wherein (b) at over 100 P Pressure and f no least one amine: mu or Carbox r h S flashed carbon chains greater than 7 carbon atoms attached to g P Y 8 P a a thereto a carbon chain of at least 8 carbon atoms imdmme gmup' parting oleophilic properties to the compound, and (c) Group (V) Oleophilic Quaternary Ammonium such oleophilic amine carboxylates being the reaction In Compounds products of precursor amines having from 1 to pri- The oleophilic quaternary ammonium Compounds mary and/or secondary and/Or ternary amlpe groups are those meeting the following definition (E): and not more than 36 carbon atoms per amlne gro p, I E. The oleophilic quaternary ammonium materials and precursor carboxyllc acids having from 1 to 10 car- 5 have at least one quaternary ammonium group with boxy] groups and not overv36 carbon f from 6 to 76 carbon atoms and have at least one quaggi i li igg g g ggi g g g z ggs g ternary ammonium group attached to a substituent of boiling point if water at atmgspheric gressure at least carb9n atoms i not than 36 carbon Oleophilic amine carboxylates meeting the definition atoms lmpamng Oleophilic properties to the com- (D) are exemplified by the following categories pound Oleophilic quaternary ammonium compounds meet- D l. The reaction products of any one or more meming this definition (E) are prepared, e.g., by reacting bers selected from categories (A) (1) through (A) (6) quaternizing agents such as alkyl halides, e.g., methyl with any one or more members selected from category chloride, methyl bromide, aralkyl halides, e.g., benzyl (B) (l). chloride, alkyl sulfonates or alkyl phosphates, e.g., di-

D 2. The reaction product of any one or more memmethyl sulfate, or the like, with amine compounds havbers selected from categories (A) (l through (A) (6) ing atleast one tertiary amine group and having at least with any one or more of the carboxylic acids having one hydrocarbon substituent which contains 6 to 36 from 1 to 10 carboxylic acid groups and having no carbon atoms and which may comprise groups of chain of over seven carbon atoms attached to any carstr ight ch i branched chain, cyclic and/or aryl conboxyl group thereof, e.g.: acetic, propionic, butyric, vafiguration, and which may include substituent groups leric, caproic, heptanoic and their isomers, oxalic, fucontaining oxygen, nitrogen, sulfur, phosphorous, fluornaric, adipic, succinic, malonic, glutaric, caproic, surine or chlorine atoms. Such quaternary ammonium beric, pimelic, hydroxyacetic, lactic, glyceric, 2- compounds, are exemplified by the following categohydroxybutanoic, and the like. ries (E) (l) to (E) (5):

D 3. The reaction products of any one or more of the E l. The quaternary ammonium compounds derived members of category (B) (1) above with any one or from tertiary monoamines such as those represented by more amines having from l to 10 primary and/or secthe formulas:

Quaternary ammonium Amine tertiary Quaternizlng agent compound R OIL-r01, methyl chloride R v N I-N-CH: o1-

R CGHACHQCI,bBUZy1Ch10l'ide- R N I [R' CH'aCaH5] Cl- RI! RI! CHg-CH; omol CHQGHI R 0 NR [0 \N/ :l 01- CHr-C2 oHzofii CHa ondary and/or tertiary amine groups and having no in which R contains 6 to 36 carbon atoms, R contains chain of more than seven carbon atoms attached to any l to 36 carbon atoms and R contains 1 to 36 carbon amine group thereof, e.g.: n-amylamine, the hexylaatoms. This category includes but is not limited to the mines, the heptylamines, ethylene diamine, the propyso quaternized products of trihexyl amine, tridodecyl lene diamines, e.g., l,3-diaminopropane, the butylene, amine, tristearyl amine, octyl-dimethyl amine, dioctyl pentylene, hexylene and heptylene diamines, the ethyl- 6O methyl amine, dodecyl dimethyl amine, didodecyl ene and propylene substituted ethylene diamines and propylene diamine and polymers of these e.g., diethylene diamine, triethylene diamine, tetraethylene triamine, pentacthylcne tetramine, hexacthylene pentamine, octaethylene heptamine and the like; monoethanolamine, diethanolamine, triethanolamine, the propanolamines, the dipropanolamines, the tripropanolamines, the hydroxy C amines, the hydroxy C amines, the hydroxy C amines, the hydroxy C amines and similar diamines and triamines having hymethyl amine, octadecyl dimethyl amine, dioctadecyl methyl amine, the mixed tertiary amines derived from fatty oils, coco dimethyl amine, dicoco methyl amine, soybean dimethyl amine, disoybean methyl amine, tallow dimethyl amine, ditallow methyl amine, and the hydrogenated or partially hydrogenated products of unsaturated tertiary amines, and the like; and the quaternization products of the long chain cyclic tertiary amines including but not limited to N-coco morpholine, N-soya morpholine, N-tallow morpholine and the like, some of which are commercially available under the trademark designations Arquad.

E 2. The quaternary ammonium compounds derived from diamines and represented by the formulas:

This category includes, but is not limited to, the quaternized products of N-coco trimethylene diamine, N-soya trimethylene diamine and N-tallow trimethylene'diamine each with a plurality, e.g., 3, 10 or 20 v moles of ethylene oxide or propylene oxide per mole of Quateramine, and the like.

Amine tertiary eh t Quaternary ammonium compound Qther yp 9 quaternary ammomum Compounds R R CHaCl R R in whlch R contains from 6 to 36 carbon atoms include the followin N-(CHz) rN N(CH2)x-N CH3]C1' 10 g (5 [m-ooNmomnNwmn I H I. CzH4OH in which R contains 6 to 36 carbon atoms, R R R contain each 1 t0 carbon atoms and X is an integer as fopexample when R CHHH, Aerosol SE, a tradefrom 1 to 18, e.g., Redicote E-ll, a trademarked prodk d product, uct (reported to have the formula identified in Table, v I V V VHD' (b) R- 00 E O2H4-N(CH )a E 3. The quaternary ammonium compounds derived 2 01- from long-chain polyethoxylated and polypropoxylated 20 L 6 amines and represented by the formulas:

Quaternizlng Tertiary amine agent Quaternary compound R CHaCl -R\ N'(CH2CH2O)x H N(CHZCHZO) H] Cl R R 0H3 /N(CH1CHgCHO)x,H N(CHzCHzCHgO) ,H] 01- R R CH3 (GH,cH,o)x,H omol ;CH2CH:O),,H R-N R-N oH,oH,0) ,H (CHzCILOM Ha )CHQCHgCHzOhJI 011301 }0H2cH=oH0) H R-N R-N (omcHzcmm H (CHQCH2CHQO)HH in which R contains 6 to 36 carbon atoms and R contains l to 36 carbon atoms and x x x x,, y,, y are each intergers from 1 to 30. This category includes but is not limited to coco amine, soybean amine, tallow amine and stearyl amine each reacted with a plurality e.g., 2, 5, 10 or 15, moles of ethylene oxide or propylene oxide per mole of amine and quaternized, and the like; e.g., those commercially available under the trademark Ethoquad.

E 4. The quaternary ammonium compounds derived from long-chain polyethoxylated and polypropoxylated diamines and represented by the formula c memo H l 4 H N l l (Amine (C-HQC H7O H Tertiary) (CHZOHQO) H (Quaternizing 2 C H: C1 Agent) CH3 CH3 CHzCHzOhH R-N-CaHuN x 201- C H2 CHzO) H (Quaternary Ammonium H20 11 0) .H Compound) in which R contains 6 to 36 carbon atoms and x, y and 2. are integers from I to 30.

as for example, when R C H Hyamine 1622, a trademark product.

as for example, when R C H Zelan, a trademark product, and other compounds prepared by reacting fatty acid amides with formaldehyde (e.g., paraformaldehyde) with a tertiary base such as pyridine, alkylpyridine or quinoline. i

nary ammonium amine compounds but do not include the oleophilic amines containing only primary, secondary and/or tertiary amine groups or their acid salts, which fall into categories (A) (l) to (A) (7) and (D) (1) to (D) (3), above.

Group (VI) Oleophilic Hydroxy Compounds The oleophilic hydroxy compounds are those meeting the following definition (F):

F. The oleophilic hydroxy compounds have from 1 to hydroxy groups and have at least one hydroxyl group attached to a chain of from 6 to 36 carbon atoms imparting oleophilic properties to the compound.

Oleophilic hydroxy compounds meeting this definition (F) are exemplified by the members of the following categories:

F l. The monoand polyols prepared by reducing the acids of category (B) (1).

F 2. Alcohols having the designated chain preparable from petroleum products, e.g., by the oxo process.

The carbon chains referred to in definitions (A) to (F) above may be alkyl, alkylene, halo alkyl and haloalkylene and may be wholly or partly of linear, branched, cyclic or aromatic configuration.

WATER SOLUBLE POLYOL MATERIALS The water soluble polyols are those meeting the following definition (G):

G. The water soluble polyols which may be employed in the present invention are those which have from 2 to 10 hydroxyl groups and a weight average molecular weight less than 5000. Water soluble polyols meeting this definition (G) are exemplified by the following categones:

G l. The glycols and polyglycols, e.g., ethylene and propylene glycols and the polymers of ethylene oxide and/or propylene oxide having less than 5000 mol. wt.

G 2. The water soluble sugars, e.g., corn, beet and cane (molasses) sugars.

G 3. The water soluble alcohol amines such as monoethanolamine, diethanolamine and triethanolamine and similar propanolamines and the like.

CARBON BLACK By the term carbon black as used herein is meant any carbon blacks suitable for use by the rubber industry and set forth under the title carbon blacks at pages 251' to 264 of the publication entitled Materials and Compounding Ingredients for Rubber, compiled by J. V. Del Gatto, published by Rubber World, 1968 and herein incorporated by reference, e.g., Philblack 0- (TM), Statex K (TM), Thermax (TM), Kosmobile 77 (TM), and the like.

PROCESSING OILS The Term processing Oils as used herein is meant rubber processing material of both liquidand solid types (if required the solids types can be converted to the liquid state for use herein with the aid of solvent or plasticizer) and include processing materials set forth under Plasticers and Softeners at pages 149 to 214 of the publication entitled Materials and Compounding Ingredients for Rubber, compiled by J. V. Del Gatto, published by Rubber World, 1968, and herein incorporated by reference and. among the types of processing materials especially suitable for use in this invention are (a) the coal tar oils and pitches e.g., Bardol (TM), Bardol B (TM); (b) the asphalts, e.g., BRH No. 2 (TM); (c) the petroleum oils including the paraffinic, naphthenic. aromatic, and highly aromatic categories, which are commercially available under trademark designations. Sunpar (TM), Sundcx (TM), Sunthene (TM), Circosol (TM), and Shellflux (TM) oils, and the like, such as Circosol 2XH (TM), Sundex 53 (TM), Shell SPX 97 (TM), Dutrex-ZO, -4l9, -726, -757, -787 (TM), and Califlux TT (TM) and other oils suitable for rubber compounding or the oil extension of synthetic rubber; (d) the coumarone-indene oils and resins, e.g., Cumar Resin RH, -P10, -T(TM); (e) the liquid ester type plasticizers, e.g., dibutyl phthalate, di-(2- ethylhexyl) phthalate, diglycol Iaurate, dibenzyl sebacate, tributoxyethyl phosphate, tricresyl phosphate and the like; (f) the phenol formaldehyde thermoplastic resins, e.g., Durez 12687, 12707 (TM) and the like; (g) the hydrocarbonresins, e.g., Neville-1X 7 82, IX 125, (TM), Para-flux, Para Resin 2457 (TM); (h) the hydrocarbon resin-coumarone indene polymers, e.g., Picco Resins (TM); (i) the pine tars and pine tar oils, rosin and rosin oils, and tall oil and its derivatives, e.g., PT- 101, PT-40l, PT-800 (TM); and the like.

ELASTOMERS (AND SOLVENTS) The solvent cements, dispersions, or solutions and the aqueous dispersions or latices of elastomers employable herein include, but are not limited to, those of the diene homopolymer rubbers such as polybutadiene, polyisoprene, polychloroprene; those of diene copolymer rubbers such as the copolymers of diene monomers and monomers containing and copolymerizable therewith through a single ethylenically unsaturated group, e.g., butadiene-styrene, butadiene-acrylonitrile or methacrylonitrile, butadiene-acrylate or methacrylate ester; and rubbery copolymers of hydrocarbon monomers with polar vinylidene (including vinyl) monomers copolymerizable therewith, elastomers from olefinsand/or cyclic olefins and/0r cyclic diolefins and- /0r dicyclic diolefins including the ethylene-propylene copolymers, the ethylenepropylene terpolymers, the ethylene-butylene copolymers and terpolymers, the butadiene-monoolefin interpolymers, the isobutyleneisoprene copolymers, and the like, elastomers from olefin oxides, poly-aromatic ethers and poly-alkyl ethers and other elastomers containing oxygen in the mole-. cule, the'fluorohydrocarbon and fluorocarbon elastomers, as well as mixtures and combinations thereof with processing oils.

The elastomers preferred to be employed in solution in the present invention include, but are not limited to, those prepared in anhydrous solvent systems e.g., with the aid of catalyst systems employing metal alkyls and- /or transition metal halides. In certain of these systems after the polymerization of the olefin and/or diolefin is complete and the catalyst has been removed, the elastomer is already in solvent solution or can readily be transferred to a solvent solution suitable for masterbatching as practiced in this invention.

In selectingthe solvent the more highly volatile hydrocarbon, or halohydrocarbon, or halocarbon solvents are desirable, e.g.,: butane, pentane, hexane, cyclohexane, methylene chloride, carbon tetrachloride, and the like.

The elastomers preferred to be employed in aqueous dispersion in the present invention include, but are not limited to, those prepared by emulsion polymerization employing anionic emulsifiers, and such elastomers may be employed in the resulting latex form. Also one may employ aqueous dispersions of elastomers formed from dry polymers by known methods.

The term water soluble acids" as used herein designates the inorganic and organic acids which are water soluble both as free acids and in the form of alkali metal or ammonium salts. Examples of such acids are hydrochloric, sulfuric, nitric, phosphoric, formic, acetic, hydroxyacetic, the chloroacetic acids, propionic, oxalic, tartaric, citric, maleic, and the like.

DESCRIPTlON OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention are set forth in the following examples which also illustrate the invention in more detail.

In these examples,the corribinations of ingredients were effected by intimate mixing in the highspeed, high shear Waring Blender, except where otherwise noted, and the beading was effected by using a cakemixer type laboratory beader except where otherwise noted. The removal of solvent from the intimate mixtures of the aqueous silica pigment compositions and the rubber-cements was accomplished by injecting the said mixtures into boiling water and the volatile solvent readily boiled off leaving a wet coagulum or wet crumb in aqueous serum, which serum was free of silica or essentially free of silica.

The invention may be employed to improve wet silica-polymer solution or aqueous dispersion masterbatching and masterbatches, using any alkaline slurry of never dried wet silica pigment containing bound alkali, and is applicable to the formation of masterbatches therewith with elastomer-organic solvent dispersions, i.e., cements, of all solvent soluble elastomers, and aqueous dispersions of all aqueously dispersible elastomers.

Silica pigments containing residual alkali suitable for masterbatching in accordance with the present invention are usually precipitated by the gradual acidulation of aqueous sodium silicate solution with the aid of carbon dioxide, and in accordance with the preferred embodiments of this invention are continuously maintained in an aqueously wet state without ever having been dried therefrom until incorporated in the processes and products of the present invention.

EXAMPLES Silica Preparation The aqueously wet never dried alkaline silica pigment employed in all the examples was prepared in a manner similar to Example 9 of US. Pat No. 3,250,594 except that the ratio of 41 Be. commercial sodium silicate (Na O/(SiO to water was approximately 1 to 4.5 by weight. The carbon dioxide was supplied to the sodium silicate with the aid ofa single submerged combustion burner up to the appearance of the Tyndall effect and with two such burners thereafter. The use of the submerged combustion burners was according to US. Pat. No. 3,372,046. The silica product was filtered and washed to reduce the soluble salts to the range of l to 2 percent and the filter cake had a solids of approximately l percent by weight. The resulting aqueously wet silica pigment was designated wet alkaline silica pigment-l, and had a bound and residual alkali content of about 1.5 percent by weight as Na- O, and a serum pH of about 8.5 (8.5 to 9.5).

A portion of this alkaline silica filter cake was slurried with about a half volume of water and was acidified to a pH of 4.5 with dilute sulfuric acid and as a filter cake, with washing to a filtrate pH of about 7 to 7.5.

. had a solids of approximately 10 percent by weight.

The resulting aqueously wet silica slurry was designated wet silica pigment-ll.

The just described filter cakes having a solids content of about 10 percent by weight are embraced within the term wet silica pigment (which herein connotes aqueously wet silica pigment) as are wet pigments of more reduced water content which can be prepared by pressing the said filter cakes, or of augmented water content, e.g., slurries having less than 10 percent solids content, and the terms aqueously wet silica pigment or aqueously wet state, as employed herein are gerfefieto all such" conditions Thus iii'ese'ferms as employed herein embrace aqueously wet silica pigment materials havinga solids content in the range of about 1 percent to about 65 percent solids, dry basis, by weight; however, for economy in the practice of the invention wet silica pigments of reduced water content (solids content 8 to 36 percent) are preferred.

To determine pigment quality a portion of wet silica pigment-ll was dried at C., micropulverized and compounded as set forth in Table 1 hereof.

TABLE I Quantities Compound Ingredients: (pts. Wt.)

Butadiene-styrene copolymer" Silica pigment-ll dried Antioxidant, 2,2-methylene-bis (4-methyl-6-t.-butylphenol) Magnesium oxide Paracoumarone-indene resin Zinc oxide N-tert-butyl-2-benzothiazole-sulphenamide N,N-di-o-tolylguanidine Triethanolamine Phthalic anhydride Sulfur "SBR i502 "'Cumar Resin RH, a trademark product of Allied Chemical Corp.

The compound was aged over-night, re-milled and cured for 45 minutes at 28 F.

The physical test data for the vulcanizate so prepared with the foregoing silica pigment is set forth in Table II hereof.

TABLE ll Silica tested Hardness Tensile Modulus Elong. (in vulcanizate) (Shore A) (psi) (300%) (71) Silica Pigment-ll 72 3530 I 575 In the following tabulations of Examples the ingredients (A), (B), (C) etc. are listed in the oroder of their ment can be combined in a weight ratio of wet to dry such as to provide sufficient quantity of water (about 150 pts./l pts. pigment) to permit beading of the pigment.

Tables IV and V, examples to 10, exemplify the use for masterbatching with aqueous dispersion of elastomer.

Table VI exemplifies the inclusion of carbon black and/or processing oil with the oleophilic amine treated silicas and masterbatching with elastomer latices.

of wet silica pigment treated with oleophilic amine ma- 5 Tables III, IV, V and VI correspond to Tables VIII, terial and masterbatched with elastomer latices pre- V, IV and X, respectively, of applicants concurrently pared with anionic dispersing agent. In the event silica filed US. Pat. application (Case 48DM-2A) and for production and latex masterbatching can not be confurther examples reference may be made to examples currently carried out then the treated silica may be 1 t 4 12 t 20, 25 t 27 d 35 t 36 f id li dried and then redispersed in water to produce a slurry tion herein incorporated by reference.

TABLE III Dispersible Silica (Parts by wt.)

Example 1 2 3 4 (A) Silica Slurry Alkaline silica pigment-l,

(pH 8.5-9.5) I50 150 I50 150 Dry solids basis l5 l5 l5 Water 50 50 50 50 (B) Reagent Aqueous Solution 2% aluminum sulfate: 18 9 2% zinc sulfate 20 2% sulfuric acid 8.5 4.5 Silica slurry, pH 5.0 6.5 7.0 6.0

(C) Oleophilic Amine Material in Isopropanol 10% Armeen DMCD l0 10% Armeen 2c l5 10% Ethomeen T/l2 10% Armeen T"" 15 (D) Treated Silica Pigment (a) Filtered (X) X X X X (b) Dried(l05C-)(X) X X X X (b) The dry treated silica is especialy suitable for solution masterbatching, however, after dispersing in water such silica can be employed for latex masterhatching.

TABLE IV Polymer-Silica Masterbatch (Parts by wt.)

Example 5 6 7 (A) Silica Pigment STurry Alkaline silica pigment-I (pl-I 8.5-9 5) 150 150 I Dry solids basis l5 l5 15 Water 50 50 50 (B) Reagent-Aqueous Solution 2% sulfuric acid 25.5 25.5 25.5 Silica slurry pH* 7 7 7 *Filter cake'after washing. (C) Oleophilic Amine Material in Isopropanol 10% Duomeen T 1.5 1.5 L5 (D) Polymer Latex Butadiene-acrylonitn'le 63 l3utadiene-acrylonitrile 6 l Chloroprene 43 Dry solids basis 25 25 25 Antioxidant- 0.5 0.5 0.5 Water 180 I 200 (E) coagulant-Aqueous Solution 2% Aluminum sulfate 125 70 Water 250 250 2-50 Duomeen T; N-tallow trimethyle'ne diamine. a trademark product.

Hycar l570 20. a carboxyl-modifiedbutadiene/acrylonitrile latex, a trade mark product.

Hycar l56l. a butadiene/acrylonitrile latex, a trademark product.

I Chloroprene lfl eoprene 635 latex, a trademark product.

Antioxidant is 2,2'-methylene-bis(4-methyl-fi-t-butylphenol).

Waring blender (a trademark product).

TABLE iv Continued Polymer-Silica Masterbatch (Parts by wt.)

Example 5 6 7 (F) Coagulation Treated silica+ polymer latex and coagulant were Polymer-Silica Masterbatch (Parts by wt.)

Example 8 9 10 l l (A) Silica Pigment Slurry Alkaline silica pigment-I (pH 8.59.5) 150 150 150 150 Dry solids basis l5 15 15 Water 50 50 50 50 (B) Reagent-AqueouS Solution 10% sulfuric acid 5.1 5 l 5.1 5 l Silica slurry pH* 7 7 7 7 *filter cake after washing.

(C) Oleophilic Amine Material in lsopropanol 10% Armeen DMCD" 1.5 10% Armeen 2C" v 1.5 10% Ethomeen 7712"" 1 5 10% Dehydroabietylamine 1.5

(D) Polymer Latex Butadiene-styrene 153 153 153 153 Dry solids basis 30 3O 30 Antioxidant"'" 0.6 0.6 0.6 (1.6 Water 150 150 150 150 (E) Coagulant-Aqueous Solution 2% aluminum sulfate 70 45 Water 250 250 250 250 (F) Coagulation Added coagulant to treated silica polymer latex (X) Y X X X l X pH serum 4.5 4.5 4.5 4.5 Silica in serum none none none none (G) Masterhatch Filtered and washed (X) X X X X Dried (C) (X) X X X X "Armeen DMCD Coco dimethyl amine. a trademark product. "'Armeen 2C dicocu amine. a trademark product.

'Ethumeen T/l 2di(pulyoxyelhylene) tallow amine. a trademark product. SBR l5( 1('l.S.= 197W).

"'Antiuxidamt is ll'mwrhylenc-hiq-$-methyLG-L-hutylphenol). Aluminum sulfate A1=(SO.),.HH,O.

TABLE VI Polymer-Silica Masterbatch Including Carbon Black and/or Processing Oil (Parts by wt.)

Example ll l2 l3 14 (A) Silica Pigment Slurry Alkaline silica pigment-1 (pH 8.5-9.5) 25 25 25 25 Dry basis 2.5 2.5 I I 2.5 2.5 Water 15 i l5 l5 l5 TAB LE Vl Continued Example ll l2 l3 14 (B) Reagent-Aqueous Solution 2% Sulfuric acid 4.2 4.2 4.2 4.2

(C) Combine (A) and (B) Blend, (X) X X X X Serum PH 4.0 4.0 4.0 4.0

(D) Oleophilic Amine Material 5% Stearylamine 4.0 20% dicoco-amine** 2 0.65 20% rosin amine 3 0.50 1.5 &&in benzene (E) Combine (C) and (D) X X X X (F) Carbon Black Statex 160 4 2.5 Philblack 4 5 Thermax 4 7.5

(G) Processing Oil Sundex 2 X H 4 l l (H) Other Ingredients 5.6% Ammonia (aqueous) l Water 50 Armeen T (a trademark product) 2 Armeen 2C (a trademark product) 3 Amine D (a trademark product) 4 Trademark products.

Table VI] exemplifies the preparation ofa wet silica tions to form the masterbatches after removal of solpigment treated with oleophilic amine compounds and vent. the combining with organic solvent dispersionsof elastomers, then removing the solvent to form a master- 40 Tables VII and Vlll correspond to Tables ill and XI, batch. The amine treated wet silica can be dried prior respectively, of applicant's concurrently filed US. Pat. to masterbatching with the elastomer cement. application (Case 48DM-4A) and for further examples Table Vlll exemplifies the preparation of wet amine reference may bernadc t0 Examples 6 to'23 of said aptreated silica and combination with carbon black andp atl n r in n rp rated y f r n e. and to /or processing oil and with the elastomer solvent solu- Table VII-A, -B and -C herein.

'TAELFW Silica-Polymer Masterbatch (Parts by wt.)

Example l5 l6 l7 l8 l9 (A) Silica Pigment Slurry-Treated Oleophilic Amine Material (a) Silica Pigment Slurry Alkaline silica pigment-I (pH 8.5- 9.5) I I50 150 [50 Dry solids basis l5 l5 l5 l5 15 50 50 50 50 50 Water TABLE VII-Continued Silica-Polymer Masterbatch (Parts by wt.)

Example 15 l6 l7 l8 l9 (b) Reagent Aqueous Solution 2% Aluminum sulfate (1) 55 2% Zinc sulfate 45 2% Sulfuric acid 25,5 .2 2% Calcium chloride 39 Silica slurry pH 5.0 6.5 7.0 8.5 7.5

(c) Treated Silica Pigment Filtered (X) X X X Filter cake 12.3 128.3 134 I54 1 (d) Oleophi'lic Amine Material Armeen T 0.8 L5 Duomeen T 0.9 1.5 L0 Benzene 40 4O 4O 4O 40 (e) Blending (c) and (d) I Blender, Min. 0.5 0.5 0.5 0.5 0.5

(B) Polymer Solution (a) Polymer lsobutyleneisoprene 30 Butadienev styrene 30 30 Ethylene-propylene terpolymer 30 30 (b) Solvent Hexanc I32 I70 270 132 I32 Antioxidant"" 0.6 0.6 0.6 0.6 0.6

(c) Solvation Conditions Temp. C. 60 60 60 60 60 Time agitated. hrs. l2 l2 l2 l2 l2 (C) Blending (A) plus (B) Blenderf min. 0.5 0.5 0.5 0.5 0.5

(D) Solvent Removal Boiling water (X) X X X X X Silica separation H into water phase none none none none none (E) Masterbatch Dried (105C) (X) X X X X X 'Aluminum sulfate Al,(SO .l4H O.

'Armeen T (a trademark product) tallow amine.

Duomeen T (a trademark product) N-tallow trimethylene diamine.

*Waring blender (a trademark product).

*Butyl rubber 268, (a trademark product).

"Solprene 300, (a trademark product) a normal viscosity, non-staining, solution polymerized random 75/25 copolymer of butadiene and styrene.

Nordel I320. (a trademark product) a terpolymer of ethylene, propylene and a non-conjugated diene.

""The antioxidant is 2,2-methylene-bis(4-methyl-6-t.-butylphenol) ""lhe silica solvated polymer combination is dropped into boiling water to vaporize the solvent and the polymer-silica masterbatch is recovered and dried.

TKELE Vlll Silica-Polymer Masterbatch Including Carbon Black (Parts by wt.)

Example 20 2l 22 23 24 (A) Silica Pigment Slurry Alkaline silica pigment-l pH 8.5-9.5 25 25 25 25 25 Dry solids basis 2.5 2.5 2.5 2.5 2.5

Silica-Polymer Masterbatch Including Carbon Black (Parts by wt.)

Example Reagent-Aqueous Solution 2% Aluminum sulfate" 2% Calcium chloride 2% Zinc sulfate 2% Magnesium sulfate 2% Sulfuric acid Combine (A) and (B) Blend. min.

Oleophilic Amine Material 20% Stearylamine* 20% Cocoamine" 20% Dicocoamine 20% Rosin amine" Combine (C) and (D) Blend min.

Carbon Black and/or Processing Oil Philblack O Sundex ZXH Combine (E) and (F) Blend, min.

Combine (G) and (H) Blend min.

Solvent Removal" Boiling water (X) Silica separation in serum Masterbatch Dried 105C.) (X) pill LII

none none none III One

In solution in benzene.

"Alurninum sulfate Al (S0,) .l4H O. Waring blender, a trademark product.

"A trademark product. "Butyl rubber 268, (a trade mark product). 'Solprene 300, (a trademark product) a normal viscosity, non-staining, solution polymerized random 75/25 copolymer of butadiene and styrenev Nordel 1320, (a trademark product) a termpolymer of ethylene. propylene and a non-conjugated diene.

'"The antioxidant is 2.2-methylene-bis(4-methyI-6-t.-butylphenol).

""l'he silica-solvated polymer combination is dropped into boiling water to vaporize the solvent and the silica-carbon black-polymer masterbatch is recovered and dried.

TABLE .Vlll-A Polymer-Silica Masterbatch (Parts by wt.)

Example 24 A B C D (A) Silica Pigment Slurry Alkaline silica pigment-l (pH 9.0) 29.4 29.4 29.4 29.4 Dry solids basis 5 5 5 5 Water l5 l5 l5 15 (B) Reagent-Aqueous Solution 7 2% sulfuric acid l5 l5 Treated silica pH 4.0 4.0 Filtered (X) X X Filter cake Dry solids. 7r l2.2 12.2 Quantity. wet wt. 41 41 Water l0 l0 l0 l0 Polymer-Silica Masterbatch (Parts by wt.)

Example 24 A B C D (C) Oleophiliclmidazoline Compound in lsopropanol 10% Varine O" 1 10% Finazolene MS l 10% Finazolene S acetat 1 10% Finazolene CY sulfate 1 (D) Polymer Latex Butadiene-styrene"" 55.5 55.5 55.5 55.5

Dry solids basis l 10 10 10 Antioxidant 0.2 0 2 0.2 02

Water 50 50 50 50 (E) CoagulantAqueous Solution 2% sulfuric acid 7 6 l3 Sat. sodium chloride 7 6 l3 2% aluminum sulfate" 25 (F) Coagulation Added coagulant to treated silica polymer latex (X) X X X X pH serum 5.5 5 4.5 4.0

Silica in serum none none none none (G) Masterbatch Filtered and washed (X) X X X X Dried (105C.) (X) X X X X *5 parts by wtr Finazolene T. a trademark product, an imidazoline ased on stearic acid, 2.5 pts. by wt. of 10% aqueous sulfuric acid and 37.2 pts. by wtv of water and mix until solutionclear.

Polymer-Silica Masterbatch (Parts by wt.)

Example 24- E F G (A) Silica Pigment Slurry Alkaline silica pigment-I (pH 9.0) 29.4 294 29.4 Dry solids basis 5 5 5 Water l5 15 (B) Reagent-Aqueous Solution 2% aluminum sulfate 31 2% zinc sulphate 25 2% calcium chloride l4 Treated silica slurry pH 5.0 6.4 6.8 Filtered (X) X X X Filter cake Dry solids. 16.8 17.2 17.0 Quantity. wet wt. 29 29 Water l5 l5 15 (C) Olcophilic lmidazoline Compound in lsopropanol 10% Varine C" l 10% Varin *T 1 10% Varine Cl l (D) Polymer Latex Butadiene-styrene 55.5 55.5 55.5 Dry solids basis 10 10 10 Antioxidum 0 2 0.2 0.2 Water 50 50 (E) Coagulant-Aqueous Solution 2% aluminum sulfate" 25 2% zinc sulfate 20 2% calcium chloride 25 (F) Coagulation Added coagulant to treated silica Polymer latex (X) X X X pH serum 4.5 6.2 7.0 Silica in serum none none none TABLE VIII-B-Continued Polymer-Silica Masterbatch (Parts by wt.)

Example 24- E F G ,(G) Masterbatch Filtered and washed (X) X X X Dried (105C.) (X) X X X Varine C (100% active). u trademark product. coco hydroxyethyl imiduzoline.

'Varine T (100% active). a trademark product". lull oil hydroxyethyl imiduzoline.

'Varine Cl (100% active). a trademark product, dicoco imidazoline. 'SER-ISOZ (T.Si l9.0%) "Antioxidant 2.2-methyle ne-his(4-rnethylene-6-t.-hutylphenol).

'T AELE Vin C v Treated Silica Pigment (Parts by wt.)

Example 24- l (A) Treated Silica Slurr (a) Alkaline Silica Pigment-l Quantity, wet Dry solids basis pH (8) Reactant-Aqueous Solution 2% aluminum sulfate 2% sulfuric acid 2% zinc sulfate 2% calcium chloride Combined (A) and (B) len (X Filter and wash ('X) Filter cake Dry solids, Quantity, wet wt. Dry wt.

Oleophilic lmidazoline Corn ound in [so to anol 10% Finazolene 'iA 10% Varine T 10% Varine Cl 10% Varine 0"" Combine (C) and (D) Blend (X) Carbon Black hllblack O Processin Oil Crrcosol ZXH Combine (E) with (F) and/or (G) Blend (X) Wet product, wt.

Drv Treated Silica Dry at 105C. (X) Dry Product, wt.

s; A111 LIIQO "Al,(SO .14H,O *A modified amino ethyl imidazoline based on tallow. See footnotes Table l "'A trademark product Table IX, Examples 2 5 to 28, exemplify the treatment of wet silica pigment with oleophilic quaternary ammonium compounds and these so treated silicas are especially suitable for elastomer latex masterbatching. The quaternary ammonium treated silicas when dried are also useful in preparing masterbatches from elastomer solvent solutions.

Table X, Examples 29 to 31, and Table Xl, Examples 32 to 34, further exemplify the preparation of oleophilic quaternary ammonium treated silicas and the masterbatching with various elastomer latices.

Table Xll, Examples 35 to 38, exemplify the blending and interaction of oleophilic quaternary ammonium treated wet silica and carbon black and/or processing TABLE IX Dispersible Silica (Parts by wt.) Example 25 26 27 28 (A) Silica Slurrv Alkaline silica pigment-l (pH 8.5) 150 150 150 150 Dry solids basis 15 15 15 Water 50 50 50 50 (B) Reagent Aqueous Solution 2% aluminum sulfate 18 2% zinc sulfate 2% sulfuric acid Silica slurry, pH 5.0 6.5

(C) Oleophilic Quaternary Ammonium Compound Arquad C-SO 1.0 2.0 Arquad T-50 1.5 3.0

(D) Treated Silica Pigment (a) Filtered (X) X X X (b) Dried (105C.) (X) X X X "Arquad C-50 Cocotrimethyl quaternary ammonium chloride 50% active. a trademark product, in isopropanol. "Arquad T-50 tallow-trimethyl quaternary ammonium chloride 50% active. a trademark product, in isopropanol. (a) Provides treated wet silica suitable for masterbatching and in selected combination with (b) dry silica provides composition suitable for beading.

(b) The dry treated silica is especially suita le for solution masterbatching. however. after dispersing in water such silica can be employed for latex materbatching.

Polymer-Silica Masterbatch (Parts by wt.)

Example 30 31 (A) Silica Pi ment Slurr Allzalme silica pigment-l (pH 8.5) 150 150 150 Dry solids basis 15 15 15 Water 50 50 (B) Reagent-Agueous Solution 10% sulfuric acid 5.1 5.1 5.1

Silica slurry pH 7 7 7 filter cake after washing. 7

(C) Oleophilic Quaternary Ammonium Com ound 10% Arquad 3-50 3.0 3.0 3.0

(D) Pol mer Latex fiutadiene-styrene 153 153 153 Dry solids basis 30 30 30 Antioxidant 0.6 0.6 0.6 Water 150 150 150 (E) Coagulant-Agueous Solution 2% aluminum sulfate 2% calcium chloride 80 2% sulfuric acid 40 Water 500 500 500 (F) Coa ulation Treated silica, polymer latex and then coagulant were continuously combined (X) X X X pH serum 4.5 6. 8 3.5 Silica in serum none none none G Masterbatch Filtered and washed (X) X X X Dried (C.) (X) X X X "Arquad S-50, a trademark product, soya trimethyl ammonium chloride, 50% active in isoprupanol. SBR-15O2 (T.S. 19.7%). ""Antioxidant is 2,2-methylene-bis(4-methy1-6-t.-butylpheno1).

TABLEXI Polymer-Silica Master-batch (Parts by wt.)

Example (A) Silica Pi ment Slurr Alkaline silica pigment-l (pH 8.5) 150 I50 I50 Dry solids basis l l5 Water 50 50 50 (B) Reagent-Agueous Solution 10% sulfuric acid 5.1 5.l 5l Silica slurry, pH* 7 7 7 *filter cake after washing.

(C) Oleophilic Quaternary Ammonium Com ound 10% Arquad 2075" 2 2 2 (D) Pol mer Latex Eutadlerte-acrylonitrile 63 Butadiene-acrylonitrile 61 Chloroprene 43 Dry solids basis 25 25 Antioxidant 0.5 0.5 I 0.5 Water 180 180 180 (E) Coa ulant-A ueous Solution 2% aluminum sulfate 100 85 75 Water 500 500 500 (F) Coa ulation Added treated silica plus polymer latex to (G) Masterbatch Filtered and washed (X) X Dried (105C.) (X) X 'Masterhatch balled-up.

X X X X "'Arquad 2C-75. a trademark product. .dicoco dimethyl ammonium chloride in isopropanol. "'Hycar I570 X 20. a trademark product which is a carboxyl-modified butadiene/acrylonitrile latex. "Hycar l56l, a trademark product which is a but-adiene/acrylonitrile latex.

'Neoprene 635 latex. a trademark product.

TABLE XII Polymer-Silica Masterbatchlncludin Carbon Black and Processing Oil (Parts by wt.) Examples 36 37 3.8

(A) Silica Pigment Slurry Alkaline silica pigment-l pH 8.5-9.5 25 25. 25 25 Dry basis 2.5 2.5 2.5 2.5 Water 6O 60 60 (B) Reagent Agueous Solution 2% Aluminum sulfate 8.5 8.5 2% Calcium chloride 5.0 5.0

(C) Oleophilic Quaternary Ammonium Compound Arquad C-50 v 0.1 0.l

(D) Combine (A) and (B) then C Blend, Min. 0.5 0.5 0.5 0.5

(E) Carbon Black and/or Processin Oil Philblack 6 2.5 2.5 2.5 2.5

Sundex 2XH"'" l v (F) Combine (D) and (E) Blend Min. 0.5 0.5 0.5 0.5

(G) Polymer Latex Polychloroprene l7.3 Butadiene-acrylonitrile" 24.4 Butadiene-styrene 50.6 50.6 Dry Solids 10 10 l0 l0 Water 3O 30 30 28% Ammonia, aqueous l Antioxidant 0.2 0.2 0.2 0.2 

1. A PROCESS FOR PREPARING PIGMENT COMPOSITION WHICH COMPRISES, IN COMBINATION: A. PROVIDING 10 WEIGHT PARTS, DRY BASIS, OF AQUEOUSLY WET HYDRATED SILICA PIGMENT PRECIPITATE WHICH HAS A BOUND ALKALI CONTENT IN THE RANGE OF 0.1 TO 10 PERCENT BY WEIGHT AS NA2O; WHICH HAS BEEN PREPARED BY PRECIPIPITATION FROM AN AQUEOUS SOLUTION OF ALKALI METAL SILICATE WITH THE AID OF CARBON DIOXIDE; AND WHICH HAS CONTINUOUSLY BEEN MAINTAINED IN AN AQUEOUSLY WET STATE WITHOUT HAVING BEEN DRIED THEREFROM AFTER ITS PRECIPITATION; B. PRIVIDING FROM 0.1 TO 2 WEIGHT PARTS, DRY BASIS, OF OLEOPHILIC MATERIAL SELECTED FROM THE CLASS CONSISTING OF THE MEMBERS OF THE FOLLOWING GROUPS: (1) THE OLEOPHILIC AMINES; (II) THE OLEOPHILIC CARBOXYLIC ACIDS AND THEIR ALKALI METAL AND AMMONIUM SALTS; (III) THE OLEOPHILIC CARBOXYLIC ACID SALTS OF ALUMINUM, ZINC, THE ALKALINE EARTH METALS, AND SUCH WITH AMONIUM HYDROXIDE; (IV) THE OLEOPHILIC AMINE CARBOXYLATES; (V) THE OLEOPHILIC QUATERNARY AMMONIUM COMPOUNDS, (Vi) THE OLEOPHILIC HYDROXY COMPOUNDS; (VII) THE COMBINATIONS OF 2 OR MORE MEMBERS OF THE FOREGOING GROUPS; AND FROM 0 TO 1 WEIGHT PART OF POLYOL DRY BASIS;
 2. A process as claimed in claim 1, wherein g. following step (f) the pigment composition is dried.
 3. A process as claimed in claim 1, wherein g. following step (f) the pigment composition is beaded and dried.
 4. A process as claimed in claim 3, wherein step (f) is practiced in two parts, the pigment from one part of step (f) being supplied to step (g) in the still aqueously wet state, and the pigment from the other part of step (f) being at least partially dried and being supplied to step (g) in such dried state, the weight ratio of the wet and dried silica pigments being such as to provide a sufficient quantity of water for beading.
 5. A pigment composition consisting essentially of the following components, dry basis by weight, distributed throughout the composition: a. 10 weight parts, dry basis, of hydrated silica pigment which has been prepared by precipitation from an aqueous alkali metal silicate solution with the aid of carbon dioxide, said hydrated silica pigment, prior to its incorporation in the composition having had from 0 to 100 percent of its alkalinity replaced by reaction with reactant material selected from the class consisting of the members of the following groups: Group (I) the water soluble salts of aluminum or zinc; Group (II) the water soluble salts of the alkaline earth metals; Group (III) the water soluble acids; and Group (IV) combinations of 2 or more members selected from Groups (I), (II) and (III) of this class; b. from 0.01 to 2 weight parts, dry basis, of oleophilic material selected from the class consisting of the members of the following groups: (I) the oleophilic amines; (II) the oleophilic carboxylic acids and their alkali metal and ammonium salts; (III) the oleophilic carboxylic acid salts of aluminum, zinc, the alkaline earth metals, and such with ammonium hydroxide; (IV) the oleophilic amine carboxylates; (V) the oleophilic quaternary ammonium compounds; (VI) the oleophilic hydroxy compounds; (VII) the combinations of 2 or more membErs of the foregoing groups; c. from 0 to 1 weight part, dry basis, of polyol; d. from 0 to 150 weight parts of carbon black; and e. from 0 to 45 percent, based on the total of (c) and (d), of processing oil.
 6. A pigment composition as claimed in claim 5, said composition being in beaded form.
 7. A wet pigment composition consisting essentially of the following components, dry basis by weight, distributed throughout the composition: a. 10 weight parts, dry basis, of aqueously wet hydrated silica pigment which has been prepared by precipitation from an aqueous alkali metal silicate solution with the aid of carbon dioxide, said hydrated pigment, prior to its incorporation in the composition, having had from 0 to 100 percent of its alkalinity replaced by reaction with reactant material selected from the class consisting of the members of the following groups: Group (I) the water soluble salts of aluminum or zinc; Group (II) the water soluble salts of the alkaline earth metals; Group (III) the water soluble acids; and Group (IV) combinations of 2 or more members selected from Groups (I), (II) and (III) of this class; b. from 0.01 to 2 weight parts, dry basis, of oleophilic material selected from the class consisting of the members of the following groups: (I) the oleophilic amines; (II) the oleophilic carboxylic acids and their alkali metal and ammonium salts; (III) the oleophilic carboxylic acid salts of aluminum, zinc, and the alkaline earth metals, and such with ammonium hydroxide; (IV) the oleophilic amine carboxylates; (V) the oleophilic quaternary ammonium compounds; (VI) the oleophilic hydroxy compounds; (VII) the combinations of 2 or more members of the foregoing groups; c. from 0 to 1 weight part of polyol dry basis; d. from 0 to 150 parts of carbon black; and e. from 0 to 45 percent, based on the total of (c) and (d), of processing oil.
 8. A process for preparing pigment composition which comprises, in combination: a. providing 10 weight parts, dry basis, of aqueously wet hydrated silica pigment precipitate which has a bound alkali content in the range of 0.1 to 10 percent by weight as Na2O; which has been prepared by precipitation from an aqueous solution of alkali metal silicate with the aid of carbon dioxide; and which has continuously been maintained in an aqueously wet state without having been dried therefrom after its precipitation; b. providing from 0.1 to 2 weight parts, dry basis, of oleophilic material selected from the class consisting of the members of the following groups: (I) the oleophilic amines; (II) the oleophilic carboxylic acids and their alkali metal and ammonium salts; (III) the oleophilic carboxylic acid salts of aluminum, zinc, the alkaline earth metals, and such with ammonium hydroxide; (IV) the oleophilic amine carboxylates; (V) the oleophilic quaternary ammonium compounds; (VI) the oleophilic hydroxy compounds; (VII) the combinations of 2 or more members of the foregoing groups; and from 0 to 1 weight part of polyol dry basis; c. providing from 0 to 30 weight parts, dry basis, of carbon black; d. providing from 0 to 16 weight parts of processing oil; e. replacing from 0 to 100 percent of the alkalinity of the wet pigment provided in (a) by reaction with reactant selected from the class consisting of members of the following groups: Group (I) the water soluble salts of ammonium or zinc; Group (II) the water soluble salts of alkaline earth metals; Group (III) the water soluble acids; Group (IV) combinations of 2 or more members selected from Groups (I), (II) or (III); and f. combining the pigment providing by step (e) with the material provided by steps (b), (c) and (d) to provide tHe pigment composition.
 9. A process as claimed in claim 8, wherein the quantities provided in steps (c) and (d) are respectively 0 parts and at least 5 parts by weight.
 10. A pigment composition incorporating the following components, dry basis by weight, distributed throughout the composition: a. 10 weight parts, dry basis, of hydrated silica pigment which has been prepared by precipitation from an aqueous alkali metal silicate solution with the aid of carbon dioxide, said hydrated silica pigment, prior to its incorporation in the composition having had from 0 to 100 percent of its alkalinity replaced by reaction with reactant material selected from the class consisting of the members of the following groups: Group (I) the water soluble salts of aluminum or zinc; Group (II) the water soluble salts of the alkaline earth metals; Group (III) the water soluble acids; and Group (IV) combinations of 2 or more members selected from Groups (I), (II) and (III) of this class; b. from 0.01 to 2 weight parts, dry basis, of oleophilic material selected from the class consisting of the members of the following groups: (I) the oleophilic amines; (II) the oleophilic carboxylic acids and their alkali metal and ammonium salts; (III) the oleophilic carboxylic acid salts of aluminum, zinc, the alkaline earth metals, and such with ammonium hydroxide; (IV) the oleophilic amine carboxylates; (V) the oleophilic quaternary ammonium compounds; (VI) the oleophilic hydroxy compounds; (VII) the combinations of 2 or more members of the foregoing groups; c. from 0 to 1 weight part, dry basis, of polyol; d. from 0 to 30 weight parts of carbon black; and e. from 0 to 16 weight parts of processing oil.
 11. A pigment composition as claimed in claim 10, the quantities of components (d) and (e) being respectively 0 parts and at least 5 parts, by weight. 